Process for effecting hydrocarbon conversion reactions



Aug. 1, 1944. J. D. DANFORTH 2,3 4,

PROCESL? FOR EFFECTING HYDROCARBON CONVERSION REACTIONS Filed Oct. 27, 1941 HEATING HEATING ZONE ZONE a lo FIRST CONTACT ZONE 1 SECOND CONTACT ZONE l2 l3 SEPARATINGIZONE l7! Y l5 -2| FRACTIONATING ZONE ATTORNEY Patented Aug. 1, 1944 PROCESS FOR EFFECTING HYDROCARBON CONVERSION REACTIONS Joseph 1). Danforth, Chicago, 111., assignor to Universal Oil Products Company, Chicago, 111., a corporation of Delaware 5 Application October 27, 1941, Serial No. 416,613

29 Claims. (Cl. 260--683.4)

This application is a continuation-in-part of my copending application Serial No. 373,960, filed January 10, 1941.

This invention relates to a process for effecting hydrocarbon conversion reactions in the presence of a catalyst of the Friedel-Crafts type to produce branched chain saturated hydrocarbons. The reactions to which the invention refers more particularly may involve the isomerization of straight chain or moderately branched chain saturatedhydrocarbons into branched chain or more highly branched. chain saturated hydrocarbons, or the alkylation of branched chain saturated hydrocarbons by oleflns into branched chain saturated hydrocarbons of higher molecular weight, or both the isomerization and alkyla- .tion of saturated hydrocarbons simultaneously or successively. V

Isomerization reactions of the aforesaid character in the presence of a catalyst .of the Friedel- Crafts type are known to be applicable not only to a number of individual parafl'lnic hydrocarbons certain cyclo-paraflinic or naphthenic hydrocarbons, but also to hydrocarbon mixtures containing these compounds in substantial percentages. Thus the isomerization may, for example, be applied to normal butane, to individual isomerizable saturated hydrocarbons having a boiling point within or near the gasoline boiling range, and to mixtures of these hydrocarbons. Isomerization treatment may, moreover, be applied to substantially olefin-free gasoline fractions and gasolines which contain substantial amounts of straight chain paraffin hydrocarbons in addition to certain amounts of naphthenic and branched chain paraffin hydrocarbons. Isomerization of normal butane and of normally liquid paraffinic hydrocarbons, such as normal pentane, normal hexane and soforth, is frequently desirable since the isomeric branched chain parafiinic hydrocarbons obtained therefrom are more reactive chemically.

comprise the performance of the isomerization reaction in the presence of an inert gas or hydrogen.

Alkylation reactions of the aforesaid character are known to be applicable to a number of I branched chain paraffin hydrocarbons including a Fried'el-Crafts catalyst and of hydrogen halides =of substantially straight chain structure and to In the case of gasoline or gasoline fractions, isosuch as hydrogen chloride or hydrogen bromide. Alkylation reactions permit the synthesis of relatively less commonly available branched chain hydrocarbons from lower molecular weight hydrocarbons of more common occurrence. Alkylation reactions in one particular aspect permit the production-of selected highly branched paraffin hydrocarbons boiling within gasoline boiling range and distinguished by particularly high anti-knock values and therefore desirable for use as or in aviation motor fuels.

The present invention aims at an improvement in the performance of reactions of the character described above with the view to obtaining a more continuous and substantially more economical process than has hitherto been possible. The invention particularly provides for a more satisfactory utilization of the catalyst, and for reduction in catalyst loss or requirement of catalyst 'recovery experienced to an appreciable extent i the various known processes.

Principally, the present invention comprises passing a stream of fluid through a first contact zone containing a Friedel-Crafts type catalyst,

causing said streamof fluid to remove a portion of the catalyst from the first zone, maintaining a higher catalyst concentration in the first zone than in the eflluent therefrom, permitting substantially the whole of the resultant eflluent materials from the first zone to flow into a second contact zone wherein hydrocarbon material to be converted is reacted in the presence of Friedel- Crafts type catalyst, and maintaining the'flow of said effluent from the first to the second Zone at a substantially continuous and sufficient rate to maintain the reaction.

In a general way the present process is carried out by maintaining a'satisfactory concentration of an active catalyst in the second contact zone and continuously supplying thereto small increments of active catalyst from the first contact zone. The transfer of the catalyst from v the first to the second zone is efiected by means of a fluid in liquid or gaseous state which may comprise the whole or a portion of the total hydrocarbons charged to the process, or a relatively low boiling fraction of saidhydrocarbons, or a normally gaseous paraflln hydrocarbon from an external source, or a substantially inert gas or a mixture of two or more of these materials. Frequently it is desirable to have hydrogen and/or a hydrogen halide present during the reactions, and in such event hydrogen and/or hydrogen halide may also be utilized as suitable carrying fluids. first contact zone with th catalyst contained therein under conditions of temperature and pressure necessary to introduce into the carrier fluid a desired portion of the catalyst. Having, for example, aluminum chloride, which is preterred tor practising the process of the present invention, present in the first contact zone, the carrying fluid during its passage through this zone under proper conditions of temperature and pressure picks up the desired portion 01' the aimminum chloride and the resultant eflluent from the first contact zone supplies the picked-up portion of the catalyst to the second contact zone, wherein the reactions or the process are effected or completed. The selection of any particular fluid for carrying catalyst from the first zone to the second zone will depend primarily on the nature of the catalyst used and the remaining conditions under which the desired branched chain saturated hydrocarbons are to be produced from a given initial hydrocarbon material. -Various modes in which this selection may be effected are hereafter described more fully.

It is essential for obtaining optimum results in the process of the present invention that the second contact zone be filled with granular particles or shaped bodies of solid material (hereafter for the sake of brevity referred to as granular packing material) which of itself may or may not have isomerizing and/or alkylating activity but which results in the eflicient utilization within the second contact zone of the active catalyst contained in the effluent from the first contact zone. During the normal operation of the process only a small portion of the catalyst is removed by the stream of fluid at any one time from the total quantity of catalyst contained in the first contact zone and a higher catalyst concentration will prevail in the second contact zone containing granular packing material than is maintained in the efiluent flowing from the first: to the second zone.

Another feature of the invention resides in the manner ofsubstantially continuously providing freshly exposed catalyst in the reaction zone or zones of a substantially stationary or fixed reac-- tion apparatus, containing solid or liquid Friedel- Crafts catalyst, thus obviating, the necessity of mechanical agitation and like disadvantageous devices.

In both isomerization and alkylation reactions in the presence of a catalyst of the Friedel-Craits type in vaporous state it is necessary for a substantial concentration of the catalyst to be present in the reaction zone. In conventional operations the vaporous catalyst will be carried out of the reaction zone by the reaction products, and in order to secure a substantially continuous operation it would be necessary tov recycle relatively large amounts of the catalyst (frequently in the form of a sludge-like material) particularly when the reactions are carried out with the hydrocar- The carrying fluid is contacted in the bons in gaseous phase. The present process makes it possible to avoid such a requirement of separating large quantities of catalyst from the reaction products and recirculating the separated catalytic material in a cyclic passage way. A similar requirement of recirculation also exists when the reactions are carried out in liquid phase or in mixed phase, that is, where both gases and.

liquids may be simultaneously present in the reaction zone. In either case of vapor phase, liquid phase and mixed phase operations when practising the present invention, catalytic material is present in substantial quantities in the first contact zone and only a portion and, more commonly, a rather small portion of the catalyst is carried from the first contact zone to the second contact zone, which latter zone serves either to largely retain active catalyst on the packing material or to maintain a high concentration of active catalyst in the latter zone at all times during the normal progress of the process. In this manner it is rendered possible to use either the second contact zone as principal reaction zone or to use both the first and the second contact zones simultaneously as reaction zones while at the same time preventing the continuous discharge of large quantities of catalytic material from the second contact zone.

In the normal operation of the process the materials issuing from the first contact zone will be supplied in their totality to the second contact zone and no portion thereof is withdrawn from the system at any point between the first and second contact zones. When employing the second contact zone as principal reaction zone, active catalyst such as active aluminum chloride is charged to the reaction zone substantially continuously and .simultaneously with the hydrocarbon reactants so that as the catalyst retained upon the packing material decreases in activity during use, a further quantity of fresh aluminum chloride is introduced to the second zone containing the granular packing material. The granular packing material so employed may consist of porcelain, pumice, firebrlck, quartz, activated charcoal, other activated carbons, diatomaceous earth, kaolin, raw and acid-treated clays, bauxite,

alumina, silica gel, zirconia, titania, composites of silica with alumina and/or zirconia .and so forth. Any of these packing materials may also be used in some instances in the first contact zone. The alternativefilling materials are not necessarily equivalent and the particular filling or packing material employed is dependent primarily upon the hydrocarbons being treated, the temperature and pressure used and the nature and amount of the catalyst charged.

When a relatively large packed contact zone is employed, it may also be desirable to introduce the mixture of carrying fluid and catalyst to said zone at various points between the inletand outlet thereof so that the catalyst is present in exactly the optimum concentration at all points throughout the bed of granular filling material within the packed contact zone and also so that substantially no excess of the catalyst is present at the ance with the present invention, the aluminum chloride may be picked up in the first contact zone by at least a portion of the normal parafilnic hydrocarbon charge and carried thereby to the H /t,aneous ly-with the eiliuent from the first contact'zone, so as to effect substantial isomerization' to more-branched chain parafllnic hydrocarbons in the second contact zone. Hydrogen halide may be introduced together with the normal paraffin to the first contact zone containing the.

aluminum chloride, when it is desired to effect substantial isomerization to more-branched chain paraflinic hydrocarbons in said first contact zone. In the latter case the resulting mixture of normal and branched chain hydrocarbons containing aluminum chloride-may then be contacted in the second contacting zone with an olefin so that alkylation reactions will predominate in the second contact zone although some isomerization may'also occur therein. It is also within the concepts of the invention to use the first contact zone essentiallyonly as catalyst pick-up zone and to carry out simultaneously both isomerization and alkylation of parafflns in successive sections of the second contact zone containing packing material in the presence of aluminum chloride carried into said zone by a fluid such as, for example, a straight-chain parafilnic reactant. In the last mentioned mode of operation substantial proportions of the paraifinic hydrocarbons undergo isomerization into branched and more-highly branched chain hydrocarbons in the first section of the second contact zone and these branched chain hydrocarbons are readily alkylated with olefins introduced to the second contact zone at one or moreinterm'ediate points.

When aluminum chloride is the catalyst employed in the process, the first contact zone, in which aluminum chloride is picked up byone or more of the fluids used in the process is. preferably maintained at a temperature between about 65 and 180 C. under a pressure of from substantially atmospheric to approximately 35 atmospheres or more. The resulting mixture of carrying fluid and aluminum chloride is then introduced to a second contact zone which generally will be maintained at a temperature between about minus 20 C. and plus 180 C. The

temperature on the second contact zone is preferably maintained at a temperature between and 150 C. when isomerization is'the primary objective, while relatively low temperatures of the aforesaid range of -20 to +180 and particularly temperatures from about 20 to about +120 C. are preferred for effecting alkylation.

' Hydrogen chloride may also be added to the parafflnic hydrocarbon fraction charged. The hydrogen chloride may be employed in any of the modes of operation to the extent of upto about 20% of the weight of the parafllnic hydrocarbon fraction. Hydrogen may be added, if so desired, to the reaction mixture generally in a quantity of not more than about 10 mole per cent of the hydrocarbons present. When effecting alklation it is desirable that the amounts of olefinic hydrocarbons added are such that the total mixture subjected to alkylation contains between about 1 and about 25 mole per cent of olefins based upon the alklatable hydrocarbons present.

In a specific mode of effecting primarily alkylation with the aid of aluminum chloride in accordance with the invention, branched chain paraflin hydrocarbons may be employed for carrying aluminum chloride from the first contact zone and the alkylation is then eiTected in the bon material is supplied at one or more points from an outside source.

The hydrogen and/or hydrogen chloride used to assist in the isomerizing and alklating treatments may also be employed for carrying aluminum chloride to the second or packed contact zone as it is generally desirable to carry the catalyst by means of a fluid having relatively low v activity therewith.

Saturated. hydrocarbons charged or recycled in the process may also be employed for carrying the catalyst, but when used for this purpose it is desirable that the catalyst carrying fluid be substantially free from olefins and aromatic hydrocarbons since these materials tend to react with the catalyst to form sludge-like materials which interfere with proper operation of the first contact zone and thus prevent long continuous operation of the process.

While a normally gaseous paraffin or an added substantially inert gas is frequently used as the fluid to carry the catalyst to the second contact zone, or to a plurality of such zones, a liquid, or vapors of a normally liquid material, may be employed similarly. When the catalyst carrying medium is a liquid such as a relatively low-boiling normally liquid parafiinic fraction and is maintained in substantially liquid state under the conditions prevailing in the first contact zone, the aluminum chloride catalyst is dis-' solved and/or dispersed in-the carrying fiuid thus employed and the resulting solution and/or dispersion is thereafter introduced to the second contact zone containing granular packing material. In this way it is possible to maintain a relatively high concentration of catalytic material in a contactor to which more catalyst is introduced substantiallycontinuously with a liquid charge to replenish the loss of catalyst which normally Occurs and is carried away by the reaction mixture passing'therethrough.

In such modes of operation of the present process in which catalyst is removed from the first contact zone by a stream of fluid comprising hydrocarbon material to be reacted in the second contact zone, it is frequently advantageous to divide said hydrocarbon material into two port ons, to pass the first portion of the hydrocarbon material through the primary contacting zone and to bring an unheated or less heated second portion of the hydrocarbon material into contact with the hotter efiiuent from the first contact zone by introducing the said second portion to the second contact zone at any desired point or plurality of points thereof so that a reaction mixture of desired temperature is obtained. Alternatively it may be desirable to pass a, relatively cool portion of the saturated hydrocarbon material through the first contact zone and thereafter introduce the resultant effluent together with a more highly heated portion of the hydrocarbon material to the second contact zone, when it is desired to effect the reaction in the latter zone at a higher temperature than that required in the first contact zone. I

for introducing a catalyst of the FriedehCrafts type, and particularly aluminum chloride, to the second packed) zone or to a plurality of packed second contact zone, to which olefinic hydrocarcontact zones by a fluid carrying medium are not necessarily equivalent and the particular means employed in any specific case depends primarily upon the properties of the hydrocar-.

bons undergoing treatment, the nature of the catalyst and the operating conditions employed.

The features and advantages of the'present in- Referring to the drawing, a hydrocarbon frac- I tion containing normal and/or mildly-branched chain paraflinic hydrocarbons or another catalyst carrying fluid is passed through line I, heating zone 2, and line 3 to the first contact zone 4 containing aluminum chloride or another Friedel- Crafts catalyst as hereinabove set forth. When aluminum chloride is used as catalyst, this material may be present in first contactzone 4 as a solid, a liquid, as a mixture with other metal halides, or as an adsorbed layer on a carrier. From contact zone 4 the hydrocarbon fraction or other fluid charged thereto carries a minor proportion of the catalyst therefrom through line 5 to the second contact zone 6 containing a granular packing material of the kind already mentioned. I

When a hydrogen halide as hydrogen chloride is introduced through line I simultaneously with normal or mildly branched chain paraflinic hydrocarbons, a substantial amount of isomeriza- 'Alternately a substantially inert fluid may be charged through line I, heater 2, and line 3 to tion occurs in the presence of aluminum chloride When only a portion of the freshly charged normal and/or mildly-branched chain paraflinic hydrocarbon fraction is directed through line I to pick up aluminum chloride in contact zone 4, the

remainder of the charged hydrocarbon fraction the first contact zone 4 to pick up and carry a desired amount of catalyst to the second contact zone 8 to which the hydrocarbon fraction is introduced by way of line 8, heater 9, and lines In to 5 so as to use only the zone 6 as isomerizing reaction zone. Light' gases including hydrogen and hydrogen chloride recovered from the processare admitted to zone 6 by way of lines I8 and 5. With this modification of the process it is generally desirable that all of the recycled hydrogen and hydrogen chloride be directed from line I! through lines I8 and 5 to the second contact zone 6, and that none of this may be recycled from line H to line .I.

In each modification of the process as hereinabove described with reference to the drawing, the reaction product is directed from the second or packed contact zone 6 through line II to separating zone I2 in which a relatively heavy residue or sludge-like material containing partially spent aluminum chloride is separated and withdrawn through line I3 to storage or to other use. Separating zone I2 may comprise a cooling and separating chamber or other suitable devices for removing aluminum chloride from the hydrocarbon stream which is directed from zone I2 through line I4 1 0 fractionating zone I5. Such separation in zone I2 may for example be effected in a tower containing an adsorptive material through which the hydrocarbons pass and upon which the aluminum chloride is deposited and retained.

In case isomerization and alkylation have both uct removed from zone 6 through separating isintroduced through line .8 to heating zone 9 and from thence is conducted through line Ill to line 5, through which normal and branched chain paraflinic hydrocarbons are directed to the second contact zone 6. The excess of normal and mildly-branched chain hydrocarbons recovered by fractionating the products of the process are recycled through lines 2| and 8, heater 9 and line III to line 5, and thence to contact zone 6 in which alkylatable hydrocarbons are reacted with olefinic hydrocarbons to produce higher boiling branched chain paraflinic hydrocarbons of higher boiling range and high anti-knock value.

Olefinic hydrocarbons introduced to the second contact zone 5 as described may be admitted thereto at a plurality of points throughout this reaction zone in order to substantially avoid polymerization and to assist in dissipating the exothermic heat of the alkylation reaction. Fresh- 1 "therein deposited upon the packing material,

both the zone 4 and the zone 6 functioning there fore as isomeri zing reaction zones.

zone I2 is fractionated in fractionating zone I5 to separate said product into a fraction of light gases including hydrogen and hydrogen chloride, an isoparaffinic product, a residue, and a recycle stock. The fraction oflight'gases including hydrogen and hydrogen chloride is directed from fractionating zone I5 through line I6 and in part conducted to storage or other use while at least a portion of said fraction is directed through lines I1 and I8 to lines I and 5, respectively, as hereinabove set forth. An isoparaflinic product, which is the desiredproduct of the process, is withdrawn from fractionator I5 through line I9 to cooling and storage. Relatively heavy reaction products generally boiling outside of the boiling range of gasoline, are withdrawn from fractionating zone I5 through line 20 while a recycle stock comprising unconverted and incompletely converted paraffinie hydrocarbons is recycled from fractionating zone I5 through lines 2I and 8 to heating zone 9 and thence through line 5 to the second contact zone 6 where said recycle stock is subjected to further isomerization and/or alkylation treatment.

In case the process as described is applied to the isomerization of a paraifinic hydrocarbon such as, for example, normal butane, and no olefin is admitted through line I, the reaction products separated in fractionating zone I 5 comprise: light gases including hydrogen, hydrogen chloride, and small amounts of propane; isobutane; a relatively heavy residue containing pentane and higher hydrocarbons; and a fraction comprising essentially normal butane. The light gases are withdrawn through line I6 and recycled in part through line I1, the isobutane and .residue are separately withdrawn to storage through lines 19 and 20, respectively, while the unconverted normal butane may be recycled through line 2| to further isomerization treatment in contact with the aluminum chloride contained upon the packing material in the second contact zone 6, or the normal butane, if so desired, may be recycled, by means not shown, to contact with the aluminum chloride in the first contact zone 4.

In case the process 'is operated for the production of isoparafiinio hydrocarbons boiling within the gasoline boiling range b alkylation of a lower boiling isoparaffinic hydrocarbon by an olefin, the initial isoparafinic hydrocarbon may be directed, if so desired, together with additions of hydrogen chloride and/or hydrogen, through line i, heater 2, line 3, and first contact zone 4 containing aluminum chloride; the resulting efiiuent material containing aluminum chloride is commingled with recycled isoparafiin in line 5 and thence directed to the second (packed) contact zone 6 to which an olefinic hydrocarbon is admitted through line 1 to at least one point intermediate the inlet and outlet of said second contact zone. The reaction products from contact zone 6 are directed through line II to separating zone 52 from which aluminum chloride sludge is discharged through line it while the other constituents of the total reaction product are directed through line Hi to fractionating zone E5 in which separation is efiected into light gases, an alkylate boiling substantially within gasoline boiling range, a higher boiling fraction, and a recycle stock comprising essentially the unconverted isoparamn charged to the process. The light gases which contain, hydrogen chloride and hydrogen, in case these materials are employed simultaneously, are removed from the fractionating zone it: through line it") and in part may be recycled therefrom through line ll to line i and/or to line it. The alkylate of gasoline boiling range and higher boiling residue are directed to storage through lines l9 and 28, respectively, while the recycle stock, comprising essentially unconverted isoparafinic hydrocarbon, is directed through lines ill and ii to heater ii and thence through lines ill and 5 to further treatment in the secand contact zone The following examples are introduced as characteristic oi the results obtained in the present process, although these data are presented with no intention ofthereby limiting the genera-ll broad scope of the invention. 'Ihe expression hourly liquid space velocity as used in the examples signifies the passage of a given volume of hydrocarbon material, measured in liquid or liq,-

uefied'state at normal temperature, per' hour through a unit volume of reaction space. The c. c. measurements of hydrocarbon charges and products given in the examples refer to measurements of the hydrocarbon material in liquid or liquefied state.

EXAIVIPE I A mixture of 99.8 mole per cent normal butane and 0.2 mole per cent pentane was passed upwardly through a vertically elongated first contact zone containing 206 grams of granular anhydrous aluminum chloride and the efiiuent therefrom was commingled with hydrogen chloride and then directed downwardly through a vertically elongated second contact zone containing 550 cc. of formed porcelain packing material commonly known as Berl saddles. The hydrogen chloride was added at the entrance and of the till I second (packed) contact zone at a rate of 2 grams per hour while the normal butane was introduced to the process at the rate of 70 cc. per hour. Table I shows the amount of normal butane isomerized into isobutane in a number of runs in which the first contact zone and second (packed) contact zonewere maintained at different temperatures between 60 and 99 C. In each run the two contact zones were maintained under substantially equalized pressure.

. TABLE I Isomerzzatzon of n-butane in the second contact Run No.

Duration "hours" 24 24 24 24 24 24 Process conditions:

n-Butaue feed. oc./hr 70 Hourly liquid space velocity 0.1 Hydrogen chloride gins/hr" 2.0 Mole percent H01 1 7.1 Temperature, C.:

First contact zone 60 71 82 82 88 93 Second contact zoue. 88 88 88 99 99 99 Pressure .atmospheres 18 18 l8 l9 l9 19 Charge analysis, mole percent:

n-Butane 99. Pentanes 0.2 Products analysis, mole percent:

1.2 2.8 3.2 87.3 .2 51. 9 47. 3 44. 0 11.7 32.8 43.5 46.4 49.1 Pentanes 0.9 1.0 1.0 3.4 3.5 3.7

1 Constant for all runs.

The variation in amount oi isomcrization was apparently due to the variation in the quantity of aluminum chloride carried under the difierent temperature and pressure conditions) from the first contact zone into the second contact The utilization of aluminum chloride in the second contact at 99 C. was more emcient than at 38 C., particularly with small amounts of catalyst.

1113 (Silt cc.) of a hydrocarbon fraction normal butane was passed per hour upward y rough a vertically elongated steel vessel const the first contact zone containing 2% grams (1'23 cc.) of aluminum chloride particles (having average diameters or from 0.83 to 4.? mm.) at C. under a pressure of 1% atmospheres. The resulting mixture of hy= drocarbcns and aluminum chloride was directed from the top oi the first steel vessel to a similar second vessel constituting the second contact and reaction zone and containing 100 cc. of porcelain packing material (Ber! saddles of about 7 mm. maximum diameter) maintained at a temperature between about 68 and about 82 C. as indi= cated in Table H.

At the beginning of a run the iscbutane-containing fractionwas charged for from about ii to 8 hours in order to carry aluminum chloride into the second contact zone, and then ethylene and hydrogen chloride were added'simultaneously to the second contact zone to efiect alkylation of the isobutane with ethylene in the presence of aluminum chloride introduced to the secondzone. continuously during the reaction by the isobutane passing through the first contact zone to the second zone. Table 11 indicates the composi-\ -zone containing packing material.

TABLE II Alkyla tion of isobutane by ethylene in the presence of aluminum chloride introduced by the isobutane to the second contact zone Period No.

Duration .hours 27 24 24 25 18 Temp. 01 second contact zone C 66 66 66 77 82 Total charging stock composition, mole percent:

Ethylene ll. 8 13. 7 18.0 19. 17v 7 Butanes (mainly iso-)... 83. 1 81. 9 77. 1 76.3 78. 1 Hydrogen chloride. 1. 3 1.2 1. 2 1. 2 1. 1 Hydrogen 0.6 0.7 0.7 0.0 a 0.0 Propane 3. 2 3.0 3.0 3.0 3. 1 Weight balance, grams charged:

Butancs 3, 245 3, 250 2, 810 2, 650 2, 190 Ethylene 211 226 281 316 231 Liquid product:

T al grams 499 500 551 481 279 Weight percent based on ethylene charged 237 221 204 152 121 Weight percent based on ethylene reacted- 237 221 196 168 215 Distillation, vol., percent:

21-41" C 19 10 0 l2 7 41-60" C 62, 66 .74 56 63 Above 66 C 19 24 26 32 30 Olefins in exit gas, mole percent, 4 hours after start of period 0 0 3 3.8 13

The above table shows that the completeness of the alkylation reaction was afiected by the proportion of ethylene present in the reaction mixture charged together with aluminum chloride and hydrogen chloride to the second contact After a short time on test, an exit gas containing substantially no ethylene was obtained in (period 1 and the ethylene removal continued to be complete until period 4 when the ethylene concentration in the charge was increased to 18%. When the total charge contained more than 18% of ethylene, small quantities of this olefin appeared in the exit gas.

- The chief difference in the nature of the liquid hydrocarbon product obtained as the concentration of ethylene in the charge was increased,

EXAMPLE III I Several runs were made on the alkylation of isobutanejwith isobutenc in the presence or aluminum chloride in the form of a constantly renewed amount of aluminum chloride freshly carried from a first contact zone and continuously deposited u-pon formed particles of a ceramic :packing material of about 7 mm. maximum diameter contained in a second contact and reaction zone. In each runthe pressure in the two zones was substantially equalized. Good-results and under a pressure of 18 atmospheres.

were obtained when 330 cc. per hour of a liquefied fraction containing 2.2 mole per cent of propane. 79.3% isobutane, and 18.5% normal butane was pumped upwardly through the first contact zone which comprised a tubular chamber containing 200 grams (172 cc.) of aluminum chloride particles of from about 0.83 to about 4.87 mm. average diameter maintained at 82 C. and under a pressure of 18 atmospheres. The resulting mixture containing isobutane, normal butane, propane, and aluminum chloride was thereafter introduced to a second contact zone to which isobutene and hydrogen chloride were also admitted. In the different runs the second contact zone was maintained at temperatures of from 10 to +38 C. while the molal ratio of paraflin to iso- .butene was varied from 8.7 to 17.6. The results given in Table III show how the yield and quality of the alkylation product was aiiected by varying the temperature of the second contact zone and the paraffin to olefin ratio.

TABLE I11 The results given in the above table show that a decrease in the temperature of the second contact zone within the range indicated in the table improved the yield and quality of the hydrocarbon product as indicated by its bromine numher. The per cent by volume of the hydrocarbon product boiling below C. was practically the same in the five runs shown above. As shown in the table, the highest yields of. hydrocarbons boiling below 150C. were obtained at the higher molal ratios of paraflln to olefin when using relatively low temperatures in the second contact zone.

Good alkylation was obtained when the hydrogen chloride concentration was as low as 0.! mole per cent in the charging stock or, expressed differently, with as much as 6 moles of olefin per mole of hydrogen chloride.

The octane number of the total alkylate ob tained in runs 2 to 5 inclusive, measured by the C. F. R. "Motor method was approximately 87.3,

and the octane number or this total alkylate increased to 95.4 by addition 01' 1 cc. tetraethyl lead per 3.79 liters of alkylate.

EXAMPLES IV A mixture comprising 95.5 mole per cent normal butane, 0.4% isobutane, 0.2% pentanes, and 3.9% hydrogen chloride was passedupwardly through a vertically elongated first contact zone consisting of a steel reactor containing 627 grams (600 cc.) of granular anhydrous aluminum chloride maintained at a temperature of 82 C. The eilluent mixture from said first contact zone consisted of a paraflinic hydrocarbon fraction, hydrogen chloride, and aluminum chloride. In the chain paraffinic hydrocarbons.

first period otthe run referred to in Table IV the paraffinic hydrocarbon fraction of the eflluent mixture issuing from the first contact zone contained 60.3% isobutane, 30% normal butane, 5.5% propane, and 4% pentane. About 5.2 molecular proportions of said parafiinic hydrocarbon fraction and admixed hydrogen chloride and aluminum chloride was commingled with 1 molecular proportion of ethylene and the resultant commingled materials were passed into a second contact zone containing shaped particles of porcelain packing material, aid second zone being maintained at a temperature which varied from 52 C. at the top to 41 C. at the bottom. In the second contact zone, ethylene reacted with isobutane formed in the first contact zone and admitted to the second contact zone, thus forming a product substantially consisting of branched- The yield and composition of the product of the process changes as the run progressed as indicated in Table IV.

TABLE IV Production of normally liquid branched-chain hydrocarbons from normal butane and ethylone by isomem'zation in the first contact zone and alkylation in a, second contact zone Period No,

Duration hours 48 72 35 Temperature, C.:

Oi first contact zone B2 82 82 Of second contact zone, top. l 52 52 52 Of second contact zone, bottom 41 41 41 Earallinic product, weight percent based on ethylene charged 149 196 207 Distillation, volume percent:

20-40 C. frnctionnwfiun, l 32 33 l9 Fraction boiling above 65 C l 20 20 33 Total product boiling below 150 98 99 93 Bromine number of 4065 C. fraction V l l. 2 Fraction boiling above 65 (K V l O 0 2 Chlorine, weight percent of 40455 C. raction 0.0] 0. 005 0.026

The novelty and utility of the present invention can be seen from the preceding specification and examples, although neither section is intented to unduly limit its generally broad scope.

I claim as my invention:

l. A process for en'ecting hydrocarbon converreactions to "produc branched chain saturated hydrocarbons in the presence or a catalyst the whole of the resultant effluent from said first. zone to flow into a second contact zone containing a solid packing material in the form of gran ular particles, and introducing to at least one point intermediatethe inlet and the outlet of said second zone from an outside source an olefincontaining hydrocarbon fraction to efiect formation of branched chain saturated hydrocarbons by reaction or said alkylatable saturated hydro carbons with olefins in the presence of the Friedel-Crafts catalyst and packing material in said second zone.

tact zone containing aluminum chloride catalyst to form a substantial yield of alkylatable saturated hydrocarbons, causing the resultant hydrocarbon mixture comprising alkylatable saturated hydrocarbons to remove a portion of said catalyst from said first zone, maintaining a higher catalyst concentration in said first zone than in the eflluent therefrom, permitting substantially the whole of the resultant efiluent from said first zone tofiow into a second contact zone containing a solid packing material in the form of particles, and introducing to at least one point intermediate the inlet and outlet of said second zone from an outside source an olefin-containing hydrocarbon fraction to efiect formation of branched chain saturated hydrocarbons of gasoline boiling range by reaction of said alkylatable saturated hydrocarbons with olefins in the presence of the aluminum chloride catalyst and packing material in said second zone.

3. A process for effecting hydrocarbon conversion reactions to produce branched chain saturated hydrocarbons in the presence of a catalyst which comprises passing a stream of a substantially saturated hydrocarbon and hydrogen chloride through a first contact zone containing aluminum chloride catalyst to form a reaction mixture containing a substantial proportion of alkylatable saturated hydrocarbons, causing said reaction mixture to remove a portion of said catalyst from said first zone, maintaining a higher catalyst concentration in said first zone than in 4;. A process for effecting hydrocarbon conversion reactions to produce branched chain parafrln hydrocarbons in the presence of a catalyst which comprises passing a stream of a paraffin hydrocarbon and hydrogen chloride through a first contact zone containing aluminum chloride oatalyst to form a reaction mixture containing a substantial proportion of isoparaifin hydrocarbons, causing said reaction mixture to remove a portion of said catalyst from said first zone,

maintaining a higher catalyst concentration in said first zone than in the eilluent therefrom, permitting substantially the whole of the resultant efiluen-t from said first zone" to how into a second contact zone containing a solid packing material in the form of particles, and introducing to at least one point intermediate the inlet and outlet of said second zone from an outside source an olefin-containing hydrocarbon fraction to effect formation of branched chain paraffin hydrocarbons of gasoline boiling range by reaction of said isoparaffin hydrocarbons with olefins in the presence of aluminum chloride catalyst and packing material in said second zone,

5. A process for effecting hydrocarbon conversion reactions to produce branched chain paraffin hydrocarbons in the presence of a catalyst remove a portion of said catalyst from said first zone, maintaining a higher catalyst concentration in said first zone than in the efiluent therefrom, permitting substantially the whole of the resultant eiiluent from said first zone to fiow into a second contact zone containing a solid packing material in the form of particles, and introducing to at least one point intermediate the inlet and outlet of said second zone from an outside source an olefin-containing hydrocarbon fraction to effect formation of branched chain parafiln hydrocarbons of gasoline boiling range by reaction of said isoparaffin hydrocarbons with olefins' in the presence of the aluminum chloride catalyst and packing material in said second zone.

6. A process for efiecting hydrocarbon conversion reactions to produce more-branched chain paraflin hydrocarbons of gasoline boiling range in the presence of a catalyst which comprises passing a stream of a mildly-branched chain paraffin hydrocarbon and hydrogen chloride through a first contact zone containing aluminum chloride catalyst to form a reaction mixture containing a substantial proportion of more-branched chain paraffin hydrocarbons, causing said reaction mixture to remove a portion of said catalyst from said first zone, maintaining a higher catalyst concentration in said first zone than in the ellluent therefrom, permitting substantially the whole of the resultant efiluent from said first zone to flow into a second contact zone containing a solid packing material in the form of particles, and introducing to at least one point intermediate the inlet and outlet of said second zone from an outside source an olefin-containing hydrocarbon fraction to effect formation of paraflin hydrocarbonsof gasoline boiling range by reaction of said branched and more-branched chain paraflin hydrocarbons with olefins in the presence of the aluminum chloride catalyst and packing material in said second zone.

'7. A process for efiecting hydrocarbonconversion reactions to produce branched chain paraflin. hydrocarbons in the presence of a catalyst which comprises passing a stream of a parafin hydrocarbon and hydrogen chloride through a first contact zone containing aluminum chloride catalyst to form a reaction mixture containing a substantial proportion of isoparaflin hydrocarbons, causing said reaction mixture to remove a portion of said catalyst from said first zone, maintaining a higher catalyst concentration in said first zone than in the efiluent therefrom, directing substantially the whole of the resultant eilluent from the first zone to at least one point ina second contact zone containing a solid packing material, introducing to at least one point intermediate the inlet and outlet .of said second zone from an outside source an olefin-containing hydrocarbon fraction to effect alkylation of saidisoparamn hydrocarbons by olefins in the pres ence of the aluminum chloride catalyst and packing material in said second zone, recovering from the alkylation products the branched chain paraflln hydrocarbons of gasoline boilingrange, and recycling unconverted paraflin and isoparaffin hydrocarbons to further conversion in the pi esence of aluminum chloride in said first and second contact zones. v

8. A process for efiecting hydrocarbon conversion reactions to produce branched chain paraf- -fln hydrocarbons in the presence of a catalyst which comprises passing a stream of a normal paraflin hydrocarbon and hydrogen chloride through afirst contact zone containing aluminum chloride catalyst to form a reaction mixture containing a substantial proportion of isoparaflin hydrocarbons, causing said reaction mixture to remove a portion of said catalyst from said first zone, maintaining a higher catalyst concentration in said first zone than in the effiuent therefrom, directing substantially the whole of the resultant effluent from the first zone to at least one point in a second contact zone containing a solid packing material, introducing to -first zone, maintaining a higher catalyst concenat least one point intermediate the inlet and outlet of said second zone from an outside source an olefin-containing hydrocarbon fraction to effect alkylation of said isoparaflin hydrocarbons by oleflns in the presence of the aluminum chloride catalyst and packing material in said second zone, recovering from the alkylation products the branched chain parafilns of gasoline boiling range, and recycling unconverted normal paraffin and isoparafiln hydrocarbons to further conversion in the presence of aluminum chloride in said first and second contact zones.

9. A process for efiecting hydrocarbon conversion reactions to produce more-branched chain paraflln hydrocarbons in the presence of a catalyst which comprises passing a stream of a mildly-branched chain paraflin hydrocarbon and hydrogen chloride through a first contact zone containing aluminum chloride catalyst to form a reaction mixture comprising essentially mildly-t branched and more-highly branched chain paraflln hydrocarbons, causing said reaction mixture to remove a portion of said catalyst from said tration in said first zone than in the ellluent therefrom, directing substantially the whole of the resultant eflluent from the first zone to at least one point in a second contact zone containing a solid packing material, and introducing to at least one point intermediate the inlet and outlet of said second zone from an outside source an olefin-containing hydrocarbon fraction to effect alkylation of said mildly-branched and morehighly branched chain paraflin hydrocarbons by oleflns in the presence of the aluminum chloride catalyst and packing material in said second zone, recovering from the alkylation products the morebranched chain paraflins of gasoline boiling range, and recycling unconverted mildlybranched and more-highly'branched chain paraflln hydrocarbons to further conversion in the presence of aluminum chloride in said first and,

portion of said catalyst from said first zone,

maintaining a higher catalyst concentration in said first zone than in the eflluent therefrom, directing substantially the whole of the resultant eilluent from said first zone to a plurality of points in a second contact zone containing a granular solid packing material, and introducing to at least one point intermediate the inlet and outlet of said second zone from an ouwide source an olefin-containing hydrocarbon fraction to efiect alkylation of isoparafiin hydrocarbons by olefins in the presence of the aluminum chloride catalyst and packing material in said second zone.

11. A process for efiecting hydrocarbon conversion reactions to produce branched chain parafiin hydrocarbons in the presence of a catalyst which comprises passing a stream of a paraffin hydrocarbon boiling between about and about 200 C. and hydrogen chloride through a first contact zone containing aluminum chloride catalyst to form a reaction mixture containing a substantial proportion of branched chain parai fin hydrocarbons, causing said reaction mixture to remove a portion of said catalyst from said first zone, maintaining a higher catalyst concentration in said first zone than in the eiiluent therefrom, permitting substantially the whole of the resultant efiluent from said first zone to fiow into a second contact zone-containing a granular solid packing material, and introducing an olefin from an outside source to at least one point intermediate the inlet and outlet of said second zone to efiect alkylation of branched chain paratfin hydrocarbons by olefins.

12. A process for efiecting hydrocarbon conversion reactions to produce branched chain parafiin hydrocarbons in the presence of a catalyst which comprises passing a stream of a paraffin hydrocarbon and hydrogen chloride through a first contact zone containing aluminum chloride catalyst at a temperature of from about 65 2 to about 180 C. under a superatmospheric pres sure to form a reaction mixture containing a substantial proportion of isoparafiln hydrocarbons, causing said reaction mixture to remove a portion of said catalyst from said first zone, maintaining a higher catalyst concentration in said first zone than in the emuent therefrom, directing substantially the whole of the resultant efliuent from the first zone to at least one point in a second contact zone containing a solid packing material maintained ata temperature of from about -20 to than in the efiluent therefrom, directing substantially the whole'of the resultant eflluent from said first zone to a plurality of points in a second contact zone containing a granular solid packing material maintained at a temperature of from about -20 to about 12,0 C. under a superatmospheric pressure, and introducing to at least one point intermediate the inlet and outlet of 'said second. zone from an outside source an olefincontaining hydrocarbon fraction to efiect alkylation of isoparaffin hydrocarbons by olefins in the presence of the "aluminum chloride catalyst and packing material in said second zone.

14. A process for efiecting hydrocarbon conversion reactions to' produce branched chain paraffin hydrocarbons in' the presence of a catalyst which comprises passing a stream of normal butane and hydrogen chloride through a first contact zone containing aluminum chloride at a temperature of from about 65 to about 180 C. undera superatmospheric pressure to form a reaction mixture containing a substantial propertion of isobutane, causing said reaction mixture to remove a portion of said catalyst from said first zone, maintaining a higher catalyst concentration in said first zone than in the efiiuent therefrom, directing substantially the whole of the resultant eflluent from the first zone to at least branched chain parafiin hydrocarbons of gasoline boiling range, and recycling unconverted normal butane and isobutane to further conversion inthe presence of aluminum chloride in said and recycling unconverted paraffln and isoparaffin hydrocarbons to further conversion in the presence of aluminum chloride in said first and second contact zones. 13. A process for effecting hydrocarbon conversion reactions to produce branched chain paraflin hydrocarbons in the presence of a catalyst which comprises passing a stream of a paraffin hydrocarbon and hydrogen chloride through a "first contact zone containing aluminum chloride a higher catalyst concentration in said firs", zone 15 first and second contact zones.

15. A process for effecting hydrocarbon conversion reactions to Produce branched chain isobutane, causing said reaction mixture to remove aportion of said catalyst from said first zone, maintaining a higher catalyst concentration in said ,first zone than in the efliuent therefrom, directing substantially the whole of the resultant effluent from the first zone to at least one point in a second contact zone containing a solid packing material maintained at a temperature of from about --20 to about C.- undera superatmospheric pressure, introducing to at least one point intermediate the lnlet'and outlet'of said second zone from an outside source a normally gaseous olefin toiorm branched chain paraifin hydrocarbons of gasoline boiling range by alkylation of said isobutane in the presence of the ,aluminum chloride catalyst and packing material in said second zone, recovering from the alkylation products the branched chain paraflln hydrocarbons of gasoline boiling range, and recycling. unconverted normal butane and isobutane to further conversion in the presence of 1 aluminum chloride in said first and second con; tact zones.

' 16. A process for eflecting hydrocarbon conversion reactions to produce branched chain paraffin hydrocarbons in the presence of a catalyst which comprises passing a stream of normal butane and hydrogen chloride through a first contact zone containing aluminum chloride catalyst at a temperature of from about 65 to about 180 C. under a superatmospheric pressure to form a reaction mixture containing a substantial proportion of isobutane, causing said reaction mixture to remove a portion of said catalyst from said first zone, maintaining a higher catalyst concentration in said first zone than in the eflluent therefrom; directing substantially the whole of the resultant 'efliuent-from said first zone to a plurality of points in a-second contact zone containing a granular solid packing material maintained at a temperature of from about -20 to about 120 C. under a superatmospheric pressure, and introducing to at least one point intermediate the inlet and outlet of said second zone from an outside source an olefin-containing hydrocarbon fraction to effect alkylation of isobutane-by olefins in the presence of the alumi num chloride catalyst and packing material in said second zone.

17. A process for effecting hydrocarbon conversion reactions to produce branched chain paraflin hydrocarbons in the presence of a catalyst which comprises passing a stream of normal butane andhydrogen chloride through a first contact zone-containing aluminum chloride catalyst at a temperature of fronrabout65 to about 180 C. under a superatmospheric pressure to form a reaction mixture containing a substantial proportion of isobutane, causing said re:- action mixture to remove a portion of said catalyst from said first zone, maintaining a higher catalyst concentration in said first zone than in the eflluent therefrom, directing substantially the whole of the resultant efliuent from said first zone to a plurality of points in a second contact zone containing a solid packing material maintained at a temperature of from about -20 ing olefins with isoparaflins in said second zone and removing resultant reaction products from I the outlet end thereof.

19. The process of claim 18 further characterized in that said Friedel-Crafts type catalyst comprises aluminum chloride.

v 20. The process of claim 18 furtherlcharacterized in that the paraflln comprises normal butane and the olefin comprises butenes.

21. A process for the conversion of hydrocarbons which comprises passing a stream of paraffinio fluid through and in relative movement with a bulk supply of metal halide catalyst or the F'riedel-Crafts type in a first zone under conditions suchthat only a portion of said catalyst is picked up by and carried in said stream, said fluid and conditions being such that no appreciable chemical reaction is effected between the fluid and said catalyst in the first zone, introducing the catalystcontaining efliuent from said first zone and an olefinic reactant to a second zone maintained under alkylating conditions, and

form branched chain parafiin hydrocarbons of I gasoline boiling range. l

18. A process for producing more valuable products from normal and 'mildly branched chain paramns which comprises passing a stream of said paraifins at isomerizing conditions through a first contact zone containing a Friedel-Crafts type catalyst and therein isomerizing a substantial portion of said parafiins, removing a portion of the catalyst with the eiiiuent from said first zone,

introducing said efiluent to a second zone containing a solid contact mass and collecting a substantial portion of the catalyst in said efliuent on said contact .mass, simultaneously introducing olefin hydrocarbons to said second zone, reactreacting a substantial portion of said paraflinic fluid with said oleflnic reactant in said second zone in the presence of catalyst supplied thereto from the first zone.

22. The process of claim 21 further characterized in that said second zone contains a body of solid packing material upon which is deposited catalyst supplied to said second zone inthe effiuent from said first zone.

comprises passing a stream oi. normal paraffins.

through and in relative movement with a bulk supply of metal halide catalyst of the Friedel Crafts type in a first zone, isomerizing a substantial portion of the paraflins in said zone to form isoparamns, removing a portion of said catalyst with the hydrocarbon stream discharging from said zone, introducing the resultant catalyst-containing stream to a second zone maintainedunder'alkylating conditions, and reacting at least a portion of said isoparamns with olefins in said second zone in the presence of catalyst supplied thereto from the first zone.

25. The process of claim 18 further characterized in that the olefin hydrocarbon comprises,

ethylene.

26. .The process or claim 21 further character-- ized in that the reaction in said second zone is accomplished .in the presence of a hydrogen halide.

27. The process of claim 24 further characterized in that said metal halide comprises aluminum chloride and ,hydrogen chloride is supplied to said first zone.

28. The process of claim 1 further characterized in that said saturated hydrocarbon comprises a naphthenic hydrocarbon.

29. The process of claim 1 further characterized in that said saturated hydrocarbon comprises a mixture of naphthenic and parafllnic hydrocarbons.

J OSEPHD. DANFORTH. 

